US3991085A - Epoxidized dialkyl peroxides - Google Patents
Epoxidized dialkyl peroxides Download PDFInfo
- Publication number
- US3991085A US3991085A US05/536,677 US53667774A US3991085A US 3991085 A US3991085 A US 3991085A US 53667774 A US53667774 A US 53667774A US 3991085 A US3991085 A US 3991085A
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- Prior art keywords
- epoxidized
- peroxide
- accordance
- hydrogen
- epoxy
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
- C08F299/0442—Catalysts
- C08F299/045—Peroxy-compounds
Definitions
- the present invention relates to a new class of epoxidized dialkyl peroxides.
- Epoxidized acyl peroxides are disclosed in U.S. Pat. No. 3,558,665, issued Jan. 26, 1971. This is a continuation-in-part application of Ser. No. 71,406 filed Sept. 11, 1970, now abandoned.
- the peroxides of this invention have special utilities by reason of their unusual chemical structures. The foremost of these results from the epoxy groups. Having both peroxy and epoxy groups, these new compounds are unique in that they are capable of both catalyzing and cross-linking with, for example, epoxy resins.
- the presence of epoxy groups which may be derived by oxidizing ethylenically unsaturated peroxides as disclosed hereinafter, contributes the advantageous properties of an acid scavenger and stabilizer to the epoxidized derivatives.
- acid scavengers and reaction stabilizers it has been necessary to introduce acid scavengers and reaction stabilizers as separate additives to neutralize the acidic environment required during polymerization, for example, of vinyls.
- the polyfunctional epoxy peroxides of this invention are defined by the following structural formula: ##STR1## wherein p is a whole number integer of from 1 to 2; R and R" are separately selected from hydrogen or a monovalent hydrocarbon of up to 10 carbon atoms, preferably straight chained; and R' is a radical containing up to 30 carbon atoms, is attached to the peroxy linkage by a secondary or tertiary carbon atom and is selected from monovalent alkyl, aryl or arylalkyl, or comprises the divalent hydrocarbon group ##STR2## wherein m is a whole number integer of from 0 to 5, preferably, 1 to 3, n is a whole number integer of from 1 to 5, preferably 1 to 3, and o is a whole number integer of from 0 to 1, being 1 when m is 0. It is preferred that at least 2 of the R and R" be hydrogen and that R' be up to 15 carbon atoms.
- the epoxidized peroxides defined by this invention therefore, include (1) those dialkyl epoxy-containing peroxides having the following structural formula: ##STR3## wherein R and R" are as defined above and R' is a secondary or tertiary alkyl, aryl or arylalkyl group of 4 to 20 carbon atoms, preferably arylalkyl of 6 to 15 carbon atoms; and (2) those dialkyl epoxy-containing peroxides having the following structural formula: ##STR4## wherein R and R" are defined as set forth supra, and R' is a divalent, branched chain hydrocarbon that is either saturated or contains an acetylenic linkage. In either of the aforementioned structural formulas it is preferred that R and R' be limited to hydrogen and carbon atoms.
- epoxy peroxides within the scope of this invention include the following: ##SPC1##
- novel epoxy peroxides of this invention can be obtained through a number of different processes.
- an epoxy alkyl chloride can be reacted with an appropriate hydroperoxide, as set forth infra, in the examples.
- the compounds of this invention can be formed by oxidation of ethylenically unsaturated peroxide intermediates wherein the double bond ##STR5## is converted to an epoxy ##STR6## grouping through a standard epoxidation reaction employing active oxygen agents such as peracetic acid, hydrogen peroxide/acetic acid with an acid catalyst, hydrogen peroxide/formic acid without an acid catalyst and the like.
- the unsaturated polyester resin tested was commercially available under the W. R. Grace Co. trade name MR4714 which contains styrene monomer as a cross-linking monomer.
- the bath temperature was maintained at 130° C (266° F) throughout the tests.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Compounds (AREA)
Abstract
Dialkyl peroxides containing at least one epoxy grouping alpha to the peroxide linkage. Such peroxides have been found to be useful as catalysts in the preparation of heat cured polymer systems such as unsaturated polyester resins.
Description
The present invention relates to a new class of epoxidized dialkyl peroxides. Epoxidized acyl peroxides are disclosed in U.S. Pat. No. 3,558,665, issued Jan. 26, 1971. This is a continuation-in-part application of Ser. No. 71,406 filed Sept. 11, 1970, now abandoned.
The peroxides of this invention have special utilities by reason of their unusual chemical structures. The foremost of these results from the epoxy groups. Having both peroxy and epoxy groups, these new compounds are unique in that they are capable of both catalyzing and cross-linking with, for example, epoxy resins. In other applications, the presence of epoxy groups, which may be derived by oxidizing ethylenically unsaturated peroxides as disclosed hereinafter, contributes the advantageous properties of an acid scavenger and stabilizer to the epoxidized derivatives. Heretofore, it has been necessary to introduce acid scavengers and reaction stabilizers as separate additives to neutralize the acidic environment required during polymerization, for example, of vinyls. When employing the epoxy peroxides of this invention as catalysts, it is necessary to add little or none of such compounds.
Broadly, the polyfunctional epoxy peroxides of this invention are defined by the following structural formula: ##STR1## wherein p is a whole number integer of from 1 to 2; R and R" are separately selected from hydrogen or a monovalent hydrocarbon of up to 10 carbon atoms, preferably straight chained; and R' is a radical containing up to 30 carbon atoms, is attached to the peroxy linkage by a secondary or tertiary carbon atom and is selected from monovalent alkyl, aryl or arylalkyl, or comprises the divalent hydrocarbon group ##STR2## wherein m is a whole number integer of from 0 to 5, preferably, 1 to 3, n is a whole number integer of from 1 to 5, preferably 1 to 3, and o is a whole number integer of from 0 to 1, being 1 when m is 0. It is preferred that at least 2 of the R and R" be hydrogen and that R' be up to 15 carbon atoms.
The epoxidized peroxides defined by this invention, therefore, include (1) those dialkyl epoxy-containing peroxides having the following structural formula: ##STR3## wherein R and R" are as defined above and R' is a secondary or tertiary alkyl, aryl or arylalkyl group of 4 to 20 carbon atoms, preferably arylalkyl of 6 to 15 carbon atoms; and (2) those dialkyl epoxy-containing peroxides having the following structural formula: ##STR4## wherein R and R" are defined as set forth supra, and R' is a divalent, branched chain hydrocarbon that is either saturated or contains an acetylenic linkage. In either of the aforementioned structural formulas it is preferred that R and R' be limited to hydrogen and carbon atoms.
Representative examples of epoxy peroxides within the scope of this invention include the following: ##SPC1##
The novel epoxy peroxides of this invention can be obtained through a number of different processes. For example, an epoxy alkyl chloride can be reacted with an appropriate hydroperoxide, as set forth infra, in the examples. In addition, the compounds of this invention can be formed by oxidation of ethylenically unsaturated peroxide intermediates wherein the double bond ##STR5## is converted to an epoxy ##STR6## grouping through a standard epoxidation reaction employing active oxygen agents such as peracetic acid, hydrogen peroxide/acetic acid with an acid catalyst, hydrogen peroxide/formic acid without an acid catalyst and the like.
The following examples are intended to be representative of the preparation of the novel compounds of this invention.
To a three-neck round bottom flask fitted with thermometer, agitator and charging funnel was charged 121.0 grams of t-butyl hydroperoxide (75.36% - 1.0 mole) and 180.0 grams of water (10.0 moles). The mixture was cooled to 20° C using an external ice bath and 56.0 grams of potassium hydroxide (1.0 moles) was introduced. Thereafter, 92.5 grams of epichlorohydrin (2,3-epoxy propyl chloride) (1.0 moles) was added gradually over a period of about 30 minutes. The reaction, which was exothermic and required cooling, was allowed to proceed for six hours at a temperature of 30° C. Upon completion of the reaction, the mixture was cooled and allowed to phase separate and the aqueous phase discarded. The organic phase was washed twice with 100ml portions of 5 percent NaCl aqueous solution. The washed product was dried over anhydrous sodium sulfate, 89.6 grams of clear organic product was obtained (61% of theory).
Active Oxygen (by HI analysis) Found 10.06 Theory 10.96
Epoxy Oxygen (by HBr analysis) Found 10.50 Theory 10.96
Glc analysis indicated 94.6% purity with negligible amounts of starting reactants.
Sp. Gravity = 1.0919 at 25° C. Refractive Index = 1.4200 at 20° C.
To a three-neck round bottom flask fitted with thermometer, agitator and charging funnel was charged 56.1 grams of potassium hydroxide (0.5 moles) 50% aqueous and 60.0 grams of water (3.3 moles). The temperature was maintained at 20° C by external cooling and 51.5 grams of 2,5-Dimethylhexane 2,5-Dihydroperoxide, 87.5% (0.25 moles) was added. Finally, 46.8 grams of epichlorohydrin (2,3-Epoxy Propyl Chloride) (0.50 moles) was charged over a period of about 20 minutes. The reaction, which was exothermic and required cooling, was allowed to proceed for three hours at a temperature of 30° C. Upon completion of the reaction, the mixture was cooled and allowed to phase separate and the aqueous phase discarded. The organic phase was diluted with ether to aid phase separation and washed with equal portions of 5% potassium hydroxide aqueous solution, 3% sulfuric acid aqueous solution, and saturated sodium sulfate solution. The washed organic layer was filtered and vacuum stripped at 40° C (5mmHg).
Active Oxygen (KI method) Found 9.30% Theory 11.02%
Epoxy Oxygen (HBr analysis) Found 7.17% Theory 11.02%
Glc analysis indicated negligible amounts of epichlorohydrin.
Specific Gravity = 1.084 at 25° C. Refractive Index = 1.4625 at 20° C.
Employing a similar technique to that utilized in Example II, the following products were also prepared.
__________________________________________________________________________
Active Oxygen
Epoxy Oxygen
Specific
Ref.
Found
Theory
Found
Theory
Gravity
Index
Compound % % % % at 25° C
at 20° C
__________________________________________________________________________
Cumyl Peroxy 2,3
Epoxy Propane
5.15
7.68
5.82
7.68
1.084 1.5148
2,5-Dimethyl-2,5-
Diperoxy (2,3-Epoxy
Propyl) Hexyne-3
8.01
12.58
4.00
12.58
1.078 1.4709
2,7-Dimethyl-2,7-
Diperoxy (2,3-Epoxy
Propyl) Octane
8.52
10.05
5.75
10.05
1.063 1.4618
__________________________________________________________________________
A series of polymerization tests utilizing the Society of the Plastics Industry Standard Polyester Gel Test was conducted. In this test, 49.5 grams of a polyester resin and the selected amount of catalyst, such as 0.5 gram for a one percent test, are blended and placed in an oil bath maintained at constant temperature. Time to gel point, time to peak temperature, and the peak temperature were then recorded.
The unsaturated polyester resin tested was commercially available under the W. R. Grace Co. trade name MR4714 which contains styrene monomer as a cross-linking monomer. The bath temperature was maintained at 130° C (266° F) throughout the tests.
Representative data obtained is shown in the following Table I.
TABLE I
______________________________________
Gel Peak Peak Temp.
Product Time Time ° C
______________________________________
2,5-Dimethyl-2,5-Diperoxy
(2,3-Epoxy Propyl) Hexyne-3
4'15" 4'46" 196
2,5-Dimethyl-2,5-Diperoxy
(2,3-Epoxy Propyl) Hexane
3'26" 3'52" 187
t-Butyl Peroxy 2,3-Epoxy
Propane 7'00" 7'35" 184
2,7-Dimethyl-2,7-Diperoxy
(2,3-Epoxy Propyl) Octane
4'58" 5'28" 184
Cumyl Peroxy 2,3-Epoxy
Propane 5'33" 6'00" 187
______________________________________
Similar polymerization was conducted with corresponding peroxides not having an epoxy grouping present therein. The data obtained is shown in the following Table II.
TABLE II
______________________________________
Gel Peak Peak Temp.
Product Time Time ° C
______________________________________
2,5-Dimethyl-2,5-di-tert-
Butyl Peroxy Hexyne-3
9'30" 10'20" 181
2,5-Dimethyl-2,5-di-tert-
Butyl Peroxy Hexane
5'15" 5'44" 189
di-tert-Butyl Peroxide
6'10" 6'50" 189
1,4-di-tert-Butyl Peroxy
Butane 7'11" 7'51" 182
______________________________________
The improvement in gel time and peak time of the preferred groups of the novel compounds of this invention, i.e. when R' is arylalkyl or divalent was found to be particularly significant.
Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, it is understood that certain changes and modifications may be practiced within the scope of the appended claims.
Claims (14)
1. An epoxidized peroxide consisting of carbon, oxygen and hydrogen atoms and having the formula ##EQU1## wherein p is a positive whole number integer of from 1 to 2, R is selected from hydrogen or alkyl of up to 10 carbon atoms, and R' is a radical of up to 15 carbon atoms composed of carbon and hydrogen atoms attached to the peroxy linkage through a tertiary carbon atom, said R' being selected from monovalent alkyl and arylalkyl radicals when p is 1 and the following divalent radical when p is 2 ##EQU2## wherein m is a whole number integer selected from 0 to 5, n is a whole number integer of from 1 to 5, and o is a whole number integer of from 0 to 1, being 1 when m is zero.
2. An epoxidized peroxide in accordance with claim 1, wherein p is 1 and R' is arylalkyl.
3. An epoxidized peroxide in accordance with claim 1, wherein p is 1 and R is alkyl.
4. An epoxidized peroxide in accordance with claim 1, wherein p is 2.
5. An epoxidized peroxide in accordance with claim 2, wherein R' is a cumyl radical and R is hydrogen.
6. An epoxidized peroxide in accordance with claim 2, wherein R' is a cumyl radical, R is ethyl, and R" is hydrogen.
7. An epoxidized peroxide in accordance with claim 3, wherein R is CH3 --(CH2)6 --.
8. An epoxidized peroxide in accordance with claim 3, wherein R' is t-Butyl radical and R is hydrogen.
9. An epoxidized peroxide in accordance with claim 4, wherein R is hydrogen and R' is ##STR7##
10. An epoxidized peroxide in accordance with claim 4, wherein R is hydrogen and R' is ##STR8##
11. An epoxidized peroxide in accordance with claim 4, wherein R is hydrogen and R' is ##STR9##
12. An epoxidized peroxide in accordance with claim 4, wherein R is hydrogen and R' is ##STR10##
13. An epoxidized peroxide in accordance with claim 4, wherein R is hydrogen and R' is ##STR11##
14. An epoxidized peroxide in accordance with claim 1, wherein m and n are 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/536,677 US3991085A (en) | 1970-09-11 | 1974-12-26 | Epoxidized dialkyl peroxides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7140670A | 1970-09-11 | 1970-09-11 | |
| US05/536,677 US3991085A (en) | 1970-09-11 | 1974-12-26 | Epoxidized dialkyl peroxides |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US7140670A Continuation-In-Part | 1970-09-11 | 1970-09-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3991085A true US3991085A (en) | 1976-11-09 |
Family
ID=26752180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/536,677 Expired - Lifetime US3991085A (en) | 1970-09-11 | 1974-12-26 | Epoxidized dialkyl peroxides |
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| Country | Link |
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| US (1) | US3991085A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260465A (en) * | 1980-01-04 | 1981-04-07 | Stauffer Chemical Company | Photopolymerizable composition stabilized with epoxide compounds and process |
| US4338172A (en) * | 1977-02-18 | 1982-07-06 | Stauffer Chemical Company | Photopolymerizable composition stabilized with epoxide compounds and process |
| US4459192A (en) * | 1977-05-16 | 1984-07-10 | Stauffer Chemical Company | Photopolymerizable composition stabilized with epoxide compounds and process |
| US4956416A (en) * | 1988-08-18 | 1990-09-11 | Atochem North America, Inc. | Amino or hydrazino peroxides, derivatives and their uses |
| US5272219A (en) * | 1988-08-18 | 1993-12-21 | Elf Atochem North America, Inc. | Process for preparing amino or hydrazino peroxides, derivatives and their uses |
| US5304649A (en) * | 1989-01-30 | 1994-04-19 | Elf Atochem North America, Inc. | Hydroxy-peroxides useful as polymerization initiators |
| US5387654A (en) * | 1993-01-08 | 1995-02-07 | Elf Atochem North America, Inc. | Hydroxy-peroxides and their uses |
| US5710210A (en) * | 1990-09-05 | 1998-01-20 | Elf Atochem North America, Inc. | Process for polymer reactions with functionalized peroxides |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3117166A (en) * | 1959-06-01 | 1964-01-07 | Wallace & Tiernan Inc | Peroxy derivatives of 2, 5-dimethylhexane-2, 5-dihydroperoxide |
| US3214422A (en) * | 1959-08-28 | 1965-10-26 | Wallace & Tiernan Inc | Crosslinking polyethylene |
| US3558665A (en) * | 1966-03-03 | 1971-01-26 | Argus Chem | Epoxidized peroxides |
-
1974
- 1974-12-26 US US05/536,677 patent/US3991085A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3117166A (en) * | 1959-06-01 | 1964-01-07 | Wallace & Tiernan Inc | Peroxy derivatives of 2, 5-dimethylhexane-2, 5-dihydroperoxide |
| US3214422A (en) * | 1959-08-28 | 1965-10-26 | Wallace & Tiernan Inc | Crosslinking polyethylene |
| US3558665A (en) * | 1966-03-03 | 1971-01-26 | Argus Chem | Epoxidized peroxides |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4338172A (en) * | 1977-02-18 | 1982-07-06 | Stauffer Chemical Company | Photopolymerizable composition stabilized with epoxide compounds and process |
| US4459192A (en) * | 1977-05-16 | 1984-07-10 | Stauffer Chemical Company | Photopolymerizable composition stabilized with epoxide compounds and process |
| US4260465A (en) * | 1980-01-04 | 1981-04-07 | Stauffer Chemical Company | Photopolymerizable composition stabilized with epoxide compounds and process |
| US5360867A (en) * | 1988-08-18 | 1994-11-01 | Elf Atochem North America, Inc. | Process for preparing block or graft copolymers using amino or hydrazino peroxides |
| US5272219A (en) * | 1988-08-18 | 1993-12-21 | Elf Atochem North America, Inc. | Process for preparing amino or hydrazino peroxides, derivatives and their uses |
| US4956416A (en) * | 1988-08-18 | 1990-09-11 | Atochem North America, Inc. | Amino or hydrazino peroxides, derivatives and their uses |
| US5399630A (en) * | 1988-08-18 | 1995-03-21 | Elf Atochem North America, Inc. | Process for curing polymers using amino or hydrazino peroxides |
| US5457162A (en) * | 1988-08-18 | 1995-10-10 | Elf Atochem North America, Inc. | Use of amino or hydrazino peroxides in preparing and curing polymers |
| US5304649A (en) * | 1989-01-30 | 1994-04-19 | Elf Atochem North America, Inc. | Hydroxy-peroxides useful as polymerization initiators |
| US5451654A (en) * | 1989-01-30 | 1995-09-19 | Elf Atochem North America, Inc. | Hydroxy-peroxides and their uses |
| US5710210A (en) * | 1990-09-05 | 1998-01-20 | Elf Atochem North America, Inc. | Process for polymer reactions with functionalized peroxides |
| US5710213A (en) * | 1990-09-05 | 1998-01-20 | Elf Atochem North America, Inc. | Process for polymerization reactions with functionalized peroxides |
| US5723562A (en) * | 1990-09-05 | 1998-03-03 | Elf Atochem North America, Inc. | Process for polymerization reactions with functionalized peroxides |
| US5387654A (en) * | 1993-01-08 | 1995-02-07 | Elf Atochem North America, Inc. | Hydroxy-peroxides and their uses |
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